US9932284B2 - Process for the separation of 1,4-butanediol and co-products - Google Patents

Process for the separation of 1,4-butanediol and co-products Download PDF

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US9932284B2
US9932284B2 US14/892,436 US201414892436A US9932284B2 US 9932284 B2 US9932284 B2 US 9932284B2 US 201414892436 A US201414892436 A US 201414892436A US 9932284 B2 US9932284 B2 US 9932284B2
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solvent
butanediol
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present
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US20160107966A1 (en
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Kai Jürgen FISCHER
Wouter Koot
Sipke Hidde Wadman
Jean Paul Andre Marie Joseph Gishlain LANGE
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Shell USA Inc
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Shell Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form

Definitions

  • the present invention relates to a process for the separation of 1,4-butanediol and co-products
  • 1,4-butanediol (1,4-BDO) and is a valuable chemical used industrially as a solvent and in the production of elastic fibres such as elastane/spandex, polybutyrate terephthalate and derivatives of gamma butyrolactone.
  • 1,4-butanediol is produced industrially via a number of routes from petrochemical feedstocks, obtainable from fossil fuels.
  • One industrial route requires the reaction of acetylene with two equivalents of formaldehyde followed by hydrogenation of the resultant 1,4-butynediol to form 1,4-butanediol.
  • propylene oxide is converted to allyl alcohol.
  • the allyl alcohol is then hydroformylated to form 4-hydroxybutyraldehyde, which may be hydrogenated to form 1,4-butanediol.
  • Another industrial process requires maleic anhydride as a starting material and proceeds via conversion to the methyl maleate ester and subsequent hydrogenation.
  • Other traditional routes use butadiene, allyl acetate or succinic acid as starting materials.
  • 1,4-butanediol may also be produced as a side-product in a method for making tetrahydrofuran (THF) by oxidizing n-butane to crude maleic anhydride followed by catalytic hydrogenation.
  • THF tetrahydrofuran
  • a further method for obtaining 1,4-butanediol and one or more of the desirable co-products (particularly THF) from non-fossil fuel based sources involves the decarboxylation of furfural and proceeds via an intermediate such as furan.
  • Examples of reaction processes for achieving these steps can be found in Hoydonck, H. E., Van Rhijn, W. M., Van Rhijn, W., De Vos, D. E. & Jacobs, P. A. (2012) Furfural and Derivatives, in Ulmann's Encyclopedia or Industrial Chemistry (volume 16, pp 285-313), Wiley-VCH Verlag GmBH & Co. KGaA, Weinheim; Dunlop, A. P. and Peters, F.
  • Furfural A Promising Platform for Lignocellulosic Biofuels; ChemSusChem 2012, 5, 150-166 and Watson, J. M., Ind. Eng. Chem. Prod. Res. Develop., 1973, 12(4), 310.
  • Furfural may be obtained from hemicellulose via acid hydrolysis in the liquid phase as well as in the gas phase as described in WO 2002/22593 and WO 2012/041990.
  • Succinic acid is also available from bio-based resources, as described in Green Chem., 2009, 11, 13, and can be used as a starting material in the production of 1,4-butanediol as well as the other desirable co-products, such as ⁇ -butyrolactone, n-butanol and tetrahydrofuran.
  • 1,4-BDO and co-products are produced within an aqueous stream.
  • the 1,4-BDO and whichever co-products are present are purified using an energy-intensive distillation process, which may be complicated by the presence of azeotropes.
  • the present invention provides a process for the recovery of 1,4-butanediol and at least one co-product selected from ⁇ -butyrolactone, n-butanol and tetrahydrofuran from an aqueous stream, said process comprising the steps of providing the aqueous stream, providing a first solvent stream, combining said aqueous stream with said first solvent stream and recovering at least a portion of the 1,4-butanediol and at least a portion of at least one of the co-products by liquid-liquid extraction.
  • FIGS. 1, 2 and 3 are schematic diagrams of exemplary, but non-limiting, embodiments of a process for the separation of 1,4-butanediol and THF as described herein.
  • 1,4-butanediol and its desirable co-products may be recovered together from an aqueous stream by the use of a solvent in liquid-liquid extraction.
  • the separation of the solvent, 1,4-butanediol and the co-products present may then be achieved in a more facile manner than the usual separation of 1,4-butanediol, its co-products and water by a complicated multi-stage distillation process.
  • co-products refers to ⁇ -butyrolactone, n-butanol and tetrahydrofuran.
  • Other materials such as side-products and starting materials may also be present in the aqueous stream.
  • the present invention provides a process for the recovery of 1,4-butanediol and one or more of its co-products from an aqueous stream.
  • the aqueous stream suitably comprises at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 20 wt %, most preferably at least 25 wt % water based on the overall weight of the stream.
  • the aqueous stream suitably comprises at most 99.9 wt %, preferably at most 95 wt %, more preferably at most 90 wt %, most preferably at most 75 wt % water based on the overall weight of the stream.
  • the aqueous stream is the reaction product stream from a process for the production of 1,4-butanediol and/or THF in which 1,4-butanediol and at least one of its co-products are present.
  • Particularly preferred reaction product streams include those produced in the processes involving the conversion of maleic anhydride to 1,4-butanediol and/or THF, the conversion of succinic acid to 1,4-butanediol and/or THF and the conversion of furan to 1,4-butanediol and/or THF. In each case, 1,4-butanediol and one or more of its co-products will be present in the reaction product stream.
  • 1,4-butanediol or any of the co-products may be the intended major product in the reaction product stream.
  • the aqueous stream is the reaction product stream from a process for the production of 1,4-butanediol and/or THF from bio-based, i.e. non fossil fuel base, feedstocks.
  • the 1,4-butanediol is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
  • the THF if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
  • n-butanol if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
  • the GBL if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
  • the aqueous stream may comprise other desirable and non-desirable materials.
  • the nature and quantity of these other materials will depend on the process used to produce the 1,4-butanediol and the conditions used, including catalysts, reaction conditions such as temperature, pressure and saccharide concentration and starting materials.
  • the other materials present may include n-propanol as well as starting materials and other by-products.
  • the solvent in the first solvent stream suitably comprises a solvent that has a higher affinity for 1,4-butanediol and its co-products than water and shows a liquid-liquid phase split when mixed with water or saline water at appropriate process temperatures, preferably in the range of from 0 to 250° C.
  • Suitable solvents are nitrogen- or oxygen-containing hydrocarbon-based solvents with these features.
  • Preferable solvents are those with these features selected from the group of amines, alcohols, furanic compounds such as furfural, esters, ketones, aldehydes and combinations thereof, including compounds containing 2 or more of these functionalities.
  • the solvent in the first solvent stream is an amine.
  • the solvent preferably comprises a primary, a secondary, a tertiary alkyl amine, or a combination thereof.
  • suitable amines include paraffinic amines, naphthenic amines, aromatic amines, and mixtures thereof. More preferably, the amine is a tertiary amine. Even more preferably, the amine is a tertiary paraffinic amine.
  • the amine contains carbon and nitrogen atoms in a ratio of at most 8:1 (carbon:nitrogen atoms).
  • the amine contains an aliphatic cyclic group either containing the amine nitrogen or attached to the amine nitrogen.
  • the solvent is selected from the group consisting of N,N-dimethylcyclohexylamine (DMCA), methyl cyclohexyl amine, N-methyl piperidine, triethylamine, tripropylamine, or a combination thereof.
  • DMCA N,N-dimethylcyclohexylamine
  • methyl cyclohexyl amine N-methyl piperidine
  • triethylamine tripropylamine
  • the solvent in the first solvent stream is an alcohol, and more preferably it is selected from primary, secondary and tertiary C 4+ alcohols and mixtures thereof.
  • Particularly suitable alcohols include n-butanol, n-pentanol and octanols, including 2-ethylhexanol.
  • the first solvent stream may be added to or combined with the aqueous stream in any amount sufficient to allow at least a portion of the 1,4-butanediol and at least a portion of one or more of its co-products, to dissolve in the solvent. Water may also dissolve in the solvent to the extent that the 1,4-butanediol and its co-products to water ratio in the extract stream is larger than in the aqueous stream.
  • the amount of solvent in the first solvent stream added to or combined with the aqueous stream may be from 10 to 500 wt % of the total overall content of that stream.
  • the ratio of solvent in the first solvent stream to 1,4-butanedioland its co-products may be the minimum amount for exceeding the solubility limit of the solvent in the aqueous stream to less than the amount needed to dissolve the entire aqueous stream.
  • the amount of solvent in the first solvent stream added to or combined with the aqueous stream may suitably be at least 10 wt %, preferably at least 20 wt %, more preferably at least 25 wt % of the combined amount of 1,4-butanediol and its co-products in the aqueous stream.
  • the amount of solvent in the first solvent stream added to or combined with the aqueous stream may suitably be at most 2000 wt %, preferably at most 500 wt %, more preferably at most 100 wt % of the combined amount of 1,4-butanediol and its co-products in the aqueous stream.
  • the aqueous stream is combined with the first solvent stream by any method suitable for the combination of two liquid streams, including but not limited to using a stirred mixer, passing the streams through a static mixer or by agitation.
  • liquid-liquid contactors extraction units
  • extraction units are, for example, a series of mixers and settlers, agitated extraction columns, packed extraction columns, SCHEIBEL® Columns, KARR® Columns, rotating disc contactor (RDC) columns, pulsed, packed (SMVP) and sieve tray columns.
  • the two streams are combined in a counter-current extraction unit. In such a unit, the two streams are fed to the unit at points separated by at least 50% of the length, preferably substantially the entire length, of the unit and are brought into contact with each other while passing through the unit in a counter-current fashion.
  • the 1,4-butanedioland its co-products are recovered from the aqueous stream by liquid-liquid extraction after the first solvent stream has been added to or combined with said aqueous stream.
  • the first solvent stream has been added to or combined with the aqueous stream
  • at least a portion of the 1,4-butanediol and at least a portion of the co-products present may be extracted into the solvent.
  • the solvent, along with the 1,4-butanediol and the co-products may then be separated from the rest of the aqueous stream, forming a first 1,4-butanediol, co-products, and solvent rich stream (hereinafter termed the first desired material stream) and a first residual stream.
  • any salt remains dissolved in the aqueous stream so that the separation process happens without precipitation of salts.
  • the liquid-liquid extraction may be enhanced by the inclusion of a synergist.
  • suitable synergist include demulsifiers.
  • demulsifiers can be phenol-formaldehyde resins, epoxy resins, polyamines, di-epoxides or polyols.
  • the method further comprises recovering the 1,4-butanediol, the co-products present, and/or solvent from the first desired material rich stream.
  • the 1,4-butanediol, the co-products present, and/or solvent may be recovered from the first desired material stream through a distillation process. Said distillation may involve the separation of each material via any number of distillation steps with each material suitably forming either at least a part of the distillate or at least a part of the distillation bottoms depending on the other materials present in each step.
  • the solvent may be removed from the other material in the first desired material rich stream and the 1,4-butanediol and the co-products present may then be separated from each other by a different method, e.g. distillation, extraction, etc.
  • the first desired material rich stream may be distilled to form a first 1,4-butanediol rich stream, a first solvent rich stream and separate streams rich in each of the co-products present.
  • the solvent may be recycled.
  • the streams may be separated by an extractive process in which one or more of the materials are separated by extraction.
  • 1,4-butanediol and its co-products there may be one or more of 1,4-butanediol and its co-products still present in the first residual stream.
  • further 1,4-butanediol and/or any of its co-products present are then recovered from the first residual stream by the steps of providing a second solvent stream, combining the first residual stream with said second solvent stream and recovering at least a portion of any remaining 1,4-butanediol and at least a portion of at least one of any remaining co-products present in the first residual stream by liquid-liquid extraction.
  • This process may be carried out under the same or different conditions to the recovery of 1,4-butanediol and its co-products from the original aqueous stream.
  • Suitable conditions, equipment, quantities and materials may be selected from the conditions, equipment, quantities and materials detailed above as suitable for the recovery of 1,4-butanedioland its co-products from the original aqueous stream.
  • combining the first residual stream with the second solvent stream may take place in the same or a different extraction unit as the combining of the aqueous stream and the first solvent stream.
  • the 1,4-butanediol and/or any of its co-products present are recovered from the first residual stream by liquid-liquid extraction after the second solvent stream has been added to or combined with said first residual stream.
  • a portion of the 1,4-butanediol and/or any of its co-products present may be extracted into the solvent.
  • the solvent, along with the 1,4-butanediol and/or any of its co-products present may then be separated from the rest of the first residual stream, forming a second 1,4-butanediol and/or its co-products and solvent rich stream (hereinafter the second desired material rich stream) and a second residual stream.
  • Subsequent recovery of further 1,4-butanediol and/or its co-products may optionally be carried out in the same manner resulting in third and subsequent desired material rich streams and third and subsequent residual streams.
  • the method further comprises recovering the 1,4-butanediol, its co-products and/or solvent from the second, third and/or any subsequent desired material rich stream.
  • the 1,4-butanediol and/or its co-products and/or solvent may be recovered from the second, third and/or any subsequent desired material rich stream through a distillation process as described above for the first desired material rich stream.
  • one or more of the first, second, third and subsequent residual streams may be recycled for use in the process in which the 1,4-butanediol is formed. Additional advantages of such a step include the reduction of the amount of waste produced and requiring disposal and also retaining any remaining 1,4-butanediol and/or desirable co-products in the system for subsequent recovery.
  • the process of the invention is preferably carried out at a temperature of at least 5° C., more preferably at least 10° C., even more preferably at least 20° C., even more preferably at least 25° C., most preferably at least 50° C.
  • the temperature is preferably at most 250° C., more preferably at most 200° C., even more preferably at most 150° C.
  • the pressure is preferably in the range of from 0.1 to 10 MPa, more preferably in the range of from 0.1 to 2.5 MPa, even more preferably in the range of from 0.1 to 1 MPa and must suitably be high enough to avoid vaporisation of the materials.
  • aqueous stream 101 is provided to a counter-current extraction unit 102 in which it is combined with first solvent stream 103 .
  • Liquid-liquid extraction provides a first residual stream 104 and a first desired material rich stream 105 .
  • the desired material rich stream 105 is then supplied to a distillation or other separation apparatus 106 to provide a 1,4-butanediol rich stream 107 , a solvent rich stream 108 , which is optionally recycled.
  • Co-products, represented by stream 109 may be separated together or individually, i.e. stream 109 represents a GBL stream and/or a THF stream and/or an n-butanol stream.
  • the 1,4-butanediol and any of its co-products present may each be selectively removed from the aqueous stream by liquid-liquid extraction according to the process of the invention.
  • the aqueous stream comprising 1,4-butanediol and its co-products is fed into a counter-current extraction unit comprising a number of extraction stages (three are shown here for illustrative purposes).
  • the stream 201 is introduced to a first extraction stage 210 , where it is contacted in a counter-current manner with a first solvent stream 211 .
  • a first solvent rich stream 212 containing one of the desired materials present i.e. 1,4-butanediol or one of its co-products
  • the remaining aqueous stream 213 is then passed to a second extraction stage 214 .
  • the remaining aqueous stream is contacted in a counter-current manner with a second stream 215 of the solvent.
  • a second solvent rich stream 216 containing another of the desired materials present is removed and the remaining aqueous stream 217 is passed to a third extraction stage 218 .
  • the remaining aqueous stream is contacted in a counter-current manner with a third stream 219 of the solvent.
  • a third solvent rich stream 220 containing another of the desired materials present is removed and the remaining aqueous stream 221 is also removed for further purification, recycle or disposal.
  • a fourth extraction stage may be used in order to extract the fourth desired material present.
  • each extraction stage may contain one or more extraction processes.
  • which material is extracted at each point will depend on the solvent and any temperature profile present.
  • the aqueous stream comprising 1,4-butanediol and its co-products 301 is fed into a counter-current extraction unit 322 .
  • Said extraction unit is also fed with first solvent stream 323 , which is contacted with stream 301 in a counter-current manner.
  • a first solvent rich stream 312 containing one of the desired materials present, is removed.
  • a second solvent rich stream 316 containing another of the desired materials present, and a third solvent rich stream 320 , containing a third desired material are removed.
  • a residual stream 321 is also removed for further purification, recycle or disposal.
  • a fourth extraction step may be used to separate the fourth desired material present.
  • a fourth solvent rich stream, containing the fourth desired material will be removed.
  • an additional aqueous stream 324 may be added to the extraction unit 322 .
  • the residual stream 321 may then be recycled and added to aqueous stream 324 before it is fed into extraction unit 322 .
  • the feed stream 301 may be located at any height (tray) in extraction unit 322 , even below the first 312 or second 320 alcohol rich streams.
  • An aqueous stock solution was prepared containing 7.1 wt % tetrahydrofuran (THF) and 16.5 wt % 1,4-butanediol (BDO).
  • Example 1 5 gram of the stock solution described in Example 1 solution was contacted with 4 gram of dimethylcyclohexylamine. After separation of the layers, the organic and water phase were analyzed by GC. The organic phase contained 60% of the THF present and 40% of BDO present.

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Abstract

The present invention provides a process for the recovery of 1,4-butanediol and at least one co-product selected from γ-butyrolactone, n-butanol and tetrahydrofuran from an aqueous stream, said process comprising the steps of providing the aqueous stream, providing a first solvent stream, combining said aqueous stream with said first solvent stream and recovering at least a portion of the 1,4-butanediol and at least a portion of at least one of the co-products by liquid-liquid extraction.

Description

PRIORITY CLAIM
The present application is a National Stage (§ 371) application of PCT/EP2014/061149, filed May 28, 2014, which claims priority from European Application 13169992.8 filed May 31, 2013, each of which are hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to a process for the separation of 1,4-butanediol and co-products
BACKGROUND OF THE INVENTION
1,4-butanediol (1,4-BDO) and is a valuable chemical used industrially as a solvent and in the production of elastic fibres such as elastane/spandex, polybutyrate terephthalate and derivatives of gamma butyrolactone.
1,4-butanediol is produced industrially via a number of routes from petrochemical feedstocks, obtainable from fossil fuels. One industrial route requires the reaction of acetylene with two equivalents of formaldehyde followed by hydrogenation of the resultant 1,4-butynediol to form 1,4-butanediol. In an alternative process, propylene oxide is converted to allyl alcohol. The allyl alcohol is then hydroformylated to form 4-hydroxybutyraldehyde, which may be hydrogenated to form 1,4-butanediol. Another industrial process requires maleic anhydride as a starting material and proceeds via conversion to the methyl maleate ester and subsequent hydrogenation. Other traditional routes use butadiene, allyl acetate or succinic acid as starting materials.
1,4-butanediol may also be produced as a side-product in a method for making tetrahydrofuran (THF) by oxidizing n-butane to crude maleic anhydride followed by catalytic hydrogenation.
It is often the case that other desirable co-products, such as THF, γ-butyrolactone (GBL) and n-butanol are formed in processes that produce 1,4-butanediol. Such processes can be tailored to make more or less of each of these chemicals.
In recent years, increased efforts have focused on producing chemicals, including 1,4-BDO and the desirable co-products, from renewable feedstocks, such as sugar-based materials. U.S. Pat. No. 8,067,214 describes a biosynthetic pathway to produce 1,4-BDO directly from sugar using a non-naturally occurring microbial organism.
A further method for obtaining 1,4-butanediol and one or more of the desirable co-products (particularly THF) from non-fossil fuel based sources involves the decarboxylation of furfural and proceeds via an intermediate such as furan. Examples of reaction processes for achieving these steps can be found in Hoydonck, H. E., Van Rhijn, W. M., Van Rhijn, W., De Vos, D. E. & Jacobs, P. A. (2012) Furfural and Derivatives, in Ulmann's Encyclopedia or Industrial Chemistry (volume 16, pp 285-313), Wiley-VCH Verlag GmBH & Co. KGaA, Weinheim; Dunlop, A. P. and Peters, F. N., in The Furans Reinhold Publ. Co, 1953; K. J. Zeitsch, in “The Chemistry and Technology of Furfural and its Many By-products” Sugar Series 13, Elsevier, 2000; Lange, J-P, van der Heide, E, van Buijtenen, J., and Price, R.; Furfural—A Promising Platform for Lignocellulosic Biofuels; ChemSusChem 2012, 5, 150-166 and Watson, J. M., Ind. Eng. Chem. Prod. Res. Develop., 1973, 12(4), 310. Furfural may be obtained from hemicellulose via acid hydrolysis in the liquid phase as well as in the gas phase as described in WO 2002/22593 and WO 2012/041990.
Succinic acid is also available from bio-based resources, as described in Green Chem., 2009, 11, 13, and can be used as a starting material in the production of 1,4-butanediol as well as the other desirable co-products, such as γ-butyrolactone, n-butanol and tetrahydrofuran.
Many processes provide 1,4-BDO and co-products as products within an aqueous stream. Typically, the 1,4-BDO and whichever co-products are present are purified using an energy-intensive distillation process, which may be complicated by the presence of azeotropes.
It would, therefore, be advantageous to provide an improved method suitable for the recovery of at least 1,4-butanediol and its desirable co-products from aqueous streams.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a process for the recovery of 1,4-butanediol and at least one co-product selected from γ-butyrolactone, n-butanol and tetrahydrofuran from an aqueous stream, said process comprising the steps of providing the aqueous stream, providing a first solvent stream, combining said aqueous stream with said first solvent stream and recovering at least a portion of the 1,4-butanediol and at least a portion of at least one of the co-products by liquid-liquid extraction.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1, 2 and 3 are schematic diagrams of exemplary, but non-limiting, embodiments of a process for the separation of 1,4-butanediol and THF as described herein.
 DETAILED DESCRIPTION OF THE INVENTION
The present inventors have surprisingly found that 1,4-butanediol and its desirable co-products may be recovered together from an aqueous stream by the use of a solvent in liquid-liquid extraction. The separation of the solvent, 1,4-butanediol and the co-products present may then be achieved in a more facile manner than the usual separation of 1,4-butanediol, its co-products and water by a complicated multi-stage distillation process.
The term ‘co-products’ as used herein refers to γ-butyrolactone, n-butanol and tetrahydrofuran. Other materials, such as side-products and starting materials may also be present in the aqueous stream.
The present invention provides a process for the recovery of 1,4-butanediol and one or more of its co-products from an aqueous stream. The aqueous stream suitably comprises at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 20 wt %, most preferably at least 25 wt % water based on the overall weight of the stream. The aqueous stream suitably comprises at most 99.9 wt %, preferably at most 95 wt %, more preferably at most 90 wt %, most preferably at most 75 wt % water based on the overall weight of the stream.
Preferably, the aqueous stream is the reaction product stream from a process for the production of 1,4-butanediol and/or THF in which 1,4-butanediol and at least one of its co-products are present. Particularly preferred reaction product streams include those produced in the processes involving the conversion of maleic anhydride to 1,4-butanediol and/or THF, the conversion of succinic acid to 1,4-butanediol and/or THF and the conversion of furan to 1,4-butanediol and/or THF. In each case, 1,4-butanediol and one or more of its co-products will be present in the reaction product stream. It is possible that 1,4-butanediol or any of the co-products may be the intended major product in the reaction product stream. More preferably, the aqueous stream is the reaction product stream from a process for the production of 1,4-butanediol and/or THF from bio-based, i.e. non fossil fuel base, feedstocks.
The 1,4-butanediol is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
The THF, if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
The n-butanol, if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
The GBL, if present, is typically present in the aqueous stream in an amount of at least 0.1 wt %, preferably at least 5 wt %, more preferably at least 10 wt %, even more preferably at least 25 wt %, typically at most 95 wt %, preferably at most 90 wt %, more preferably at most 80 wt %, most preferably at most 75 wt %, based on the weight of the overall stream.
As well as the 1,4-butanedioland its co-products, the aqueous stream may comprise other desirable and non-desirable materials. The nature and quantity of these other materials will depend on the process used to produce the 1,4-butanediol and the conditions used, including catalysts, reaction conditions such as temperature, pressure and saccharide concentration and starting materials. Depending on the process used to produce the 1,4-butanediol, the other materials present may include n-propanol as well as starting materials and other by-products.
The solvent in the first solvent stream suitably comprises a solvent that has a higher affinity for 1,4-butanediol and its co-products than water and shows a liquid-liquid phase split when mixed with water or saline water at appropriate process temperatures, preferably in the range of from 0 to 250° C. Suitable solvents are nitrogen- or oxygen-containing hydrocarbon-based solvents with these features. Preferable solvents are those with these features selected from the group of amines, alcohols, furanic compounds such as furfural, esters, ketones, aldehydes and combinations thereof, including compounds containing 2 or more of these functionalities.
In one embodiment of the invention, preferably, the solvent in the first solvent stream is an amine. In this embodiment, the solvent preferably comprises a primary, a secondary, a tertiary alkyl amine, or a combination thereof. Examples of suitable amines include paraffinic amines, naphthenic amines, aromatic amines, and mixtures thereof. More preferably, the amine is a tertiary amine. Even more preferably, the amine is a tertiary paraffinic amine.
Preferably, the amine contains carbon and nitrogen atoms in a ratio of at most 8:1 (carbon:nitrogen atoms).
Preferably, the amine contains an aliphatic cyclic group either containing the amine nitrogen or attached to the amine nitrogen.
Most preferably, the solvent is selected from the group consisting of N,N-dimethylcyclohexylamine (DMCA), methyl cyclohexyl amine, N-methyl piperidine, triethylamine, tripropylamine, or a combination thereof.
In another embodiment of the invention, preferably, the solvent in the first solvent stream is an alcohol, and more preferably it is selected from primary, secondary and tertiary C4+ alcohols and mixtures thereof. Particularly suitable alcohols include n-butanol, n-pentanol and octanols, including 2-ethylhexanol.
The first solvent stream may be added to or combined with the aqueous stream in any amount sufficient to allow at least a portion of the 1,4-butanediol and at least a portion of one or more of its co-products, to dissolve in the solvent. Water may also dissolve in the solvent to the extent that the 1,4-butanediol and its co-products to water ratio in the extract stream is larger than in the aqueous stream. In certain embodiments, the amount of solvent in the first solvent stream added to or combined with the aqueous stream may be from 10 to 500 wt % of the total overall content of that stream.
Preferably, the ratio of solvent in the first solvent stream to 1,4-butanedioland its co-products may be the minimum amount for exceeding the solubility limit of the solvent in the aqueous stream to less than the amount needed to dissolve the entire aqueous stream. The amount of solvent in the first solvent stream added to or combined with the aqueous stream may suitably be at least 10 wt %, preferably at least 20 wt %, more preferably at least 25 wt % of the combined amount of 1,4-butanediol and its co-products in the aqueous stream. The amount of solvent in the first solvent stream added to or combined with the aqueous stream may suitably be at most 2000 wt %, preferably at most 500 wt %, more preferably at most 100 wt % of the combined amount of 1,4-butanediol and its co-products in the aqueous stream.
The aqueous stream is combined with the first solvent stream by any method suitable for the combination of two liquid streams, including but not limited to using a stirred mixer, passing the streams through a static mixer or by agitation. State of the art liquid-liquid contactors (extraction units) are, for example, a series of mixers and settlers, agitated extraction columns, packed extraction columns, SCHEIBEL® Columns, KARR® Columns, rotating disc contactor (RDC) columns, pulsed, packed (SMVP) and sieve tray columns. In a preferred embodiment of the invention, the two streams are combined in a counter-current extraction unit. In such a unit, the two streams are fed to the unit at points separated by at least 50% of the length, preferably substantially the entire length, of the unit and are brought into contact with each other while passing through the unit in a counter-current fashion.
The 1,4-butanedioland its co-products are recovered from the aqueous stream by liquid-liquid extraction after the first solvent stream has been added to or combined with said aqueous stream. For example, after the first solvent stream has been added to or combined with the aqueous stream, at least a portion of the 1,4-butanediol and at least a portion of the co-products present may be extracted into the solvent. The solvent, along with the 1,4-butanediol and the co-products may then be separated from the rest of the aqueous stream, forming a first 1,4-butanediol, co-products, and solvent rich stream (hereinafter termed the first desired material stream) and a first residual stream.
Preferably, any salt remains dissolved in the aqueous stream so that the separation process happens without precipitation of salts.
In certain embodiments, the liquid-liquid extraction may be enhanced by the inclusion of a synergist. Examples of suitable synergist include demulsifiers. Typical demulsifiers can be phenol-formaldehyde resins, epoxy resins, polyamines, di-epoxides or polyols.
Preferably, the method further comprises recovering the 1,4-butanediol, the co-products present, and/or solvent from the first desired material rich stream. The 1,4-butanediol, the co-products present, and/or solvent may be recovered from the first desired material stream through a distillation process. Said distillation may involve the separation of each material via any number of distillation steps with each material suitably forming either at least a part of the distillate or at least a part of the distillation bottoms depending on the other materials present in each step.
In one exemplary embodiment, the solvent may be removed from the other material in the first desired material rich stream and the 1,4-butanediol and the co-products present may then be separated from each other by a different method, e.g. distillation, extraction, etc.
In another exemplary embodiment, the first desired material rich stream may be distilled to form a first 1,4-butanediol rich stream, a first solvent rich stream and separate streams rich in each of the co-products present.
In each case, optionally, the solvent may be recycled.
Alternatively, the streams may be separated by an extractive process in which one or more of the materials are separated by extraction.
After carrying out the process of the invention, it is possible that there may be one or more of 1,4-butanediol and its co-products still present in the first residual stream. In one embodiment of the invention, it is preferable that further 1,4-butanediol and/or any of its co-products present are then recovered from the first residual stream by the steps of providing a second solvent stream, combining the first residual stream with said second solvent stream and recovering at least a portion of any remaining 1,4-butanediol and at least a portion of at least one of any remaining co-products present in the first residual stream by liquid-liquid extraction.
This process may be carried out under the same or different conditions to the recovery of 1,4-butanediol and its co-products from the original aqueous stream. Suitable conditions, equipment, quantities and materials may be selected from the conditions, equipment, quantities and materials detailed above as suitable for the recovery of 1,4-butanedioland its co-products from the original aqueous stream.
In this embodiment of the invention, combining the first residual stream with the second solvent stream may take place in the same or a different extraction unit as the combining of the aqueous stream and the first solvent stream.
In this embodiment of the invention, the 1,4-butanediol and/or any of its co-products present are recovered from the first residual stream by liquid-liquid extraction after the second solvent stream has been added to or combined with said first residual stream. For example, after the second solvent stream has been added to or combined with the first residual stream, a portion of the 1,4-butanediol and/or any of its co-products present may be extracted into the solvent. The solvent, along with the 1,4-butanediol and/or any of its co-products present may then be separated from the rest of the first residual stream, forming a second 1,4-butanediol and/or its co-products and solvent rich stream (hereinafter the second desired material rich stream) and a second residual stream.
Subsequent recovery of further 1,4-butanediol and/or its co-products may optionally be carried out in the same manner resulting in third and subsequent desired material rich streams and third and subsequent residual streams.
Preferably, in each case the method further comprises recovering the 1,4-butanediol, its co-products and/or solvent from the second, third and/or any subsequent desired material rich stream. The 1,4-butanediol and/or its co-products and/or solvent may be recovered from the second, third and/or any subsequent desired material rich stream through a distillation process as described above for the first desired material rich stream.
In a preferred embodiment of the invention, one or more of the first, second, third and subsequent residual streams may be recycled for use in the process in which the 1,4-butanediol is formed. Additional advantages of such a step include the reduction of the amount of waste produced and requiring disposal and also retaining any remaining 1,4-butanediol and/or desirable co-products in the system for subsequent recovery.
The process of the invention is preferably carried out at a temperature of at least 5° C., more preferably at least 10° C., even more preferably at least 20° C., even more preferably at least 25° C., most preferably at least 50° C. The temperature is preferably at most 250° C., more preferably at most 200° C., even more preferably at most 150° C. The pressure is preferably in the range of from 0.1 to 10 MPa, more preferably in the range of from 0.1 to 2.5 MPa, even more preferably in the range of from 0.1 to 1 MPa and must suitably be high enough to avoid vaporisation of the materials.
In a particularly preferred, but non-limiting, embodiment of the invention illustrated in FIG. 1, aqueous stream 101 is provided to a counter-current extraction unit 102 in which it is combined with first solvent stream 103. Liquid-liquid extraction provides a first residual stream 104 and a first desired material rich stream 105. The desired material rich stream 105 is then supplied to a distillation or other separation apparatus 106 to provide a 1,4-butanediol rich stream 107, a solvent rich stream 108, which is optionally recycled. Co-products, represented by stream 109 may be separated together or individually, i.e. stream 109 represents a GBL stream and/or a THF stream and/or an n-butanol stream.
In a further embodiment of the invention, the 1,4-butanediol and any of its co-products present may each be selectively removed from the aqueous stream by liquid-liquid extraction according to the process of the invention. In this embodiment, it will be necessary to use a solvent that has a different selectivity to each of 1,4-butanediol and its co-products present in the aqueous stream.
Selective extraction processes are demonstrated in the exemplary, but non-limiting embodiments shown in FIGS. 2 and 3.
In FIG. 2, the aqueous stream comprising 1,4-butanediol and its co-products is fed into a counter-current extraction unit comprising a number of extraction stages (three are shown here for illustrative purposes). The stream 201 is introduced to a first extraction stage 210, where it is contacted in a counter-current manner with a first solvent stream 211. A first solvent rich stream 212 containing one of the desired materials present (i.e. 1,4-butanediol or one of its co-products) is removed and the remaining aqueous stream 213 is then passed to a second extraction stage 214. In the second extraction stage 214, the remaining aqueous stream is contacted in a counter-current manner with a second stream 215 of the solvent. A second solvent rich stream 216 containing another of the desired materials present is removed and the remaining aqueous stream 217 is passed to a third extraction stage 218. In the third extraction stage 218, the remaining aqueous stream is contacted in a counter-current manner with a third stream 219 of the solvent. A third solvent rich stream 220 containing another of the desired materials present is removed and the remaining aqueous stream 221 is also removed for further purification, recycle or disposal.
If all of 1,4-butanediol, tetrahydrofuran, γ-butyrolactone and n-butanol are present in suitably high quantities, a fourth extraction stage may be used in order to extract the fourth desired material present.
In this embodiment, it will be readily understood that each extraction stage may contain one or more extraction processes. In this embodiment, which material is extracted at each point will depend on the solvent and any temperature profile present.
In a further exemplary, but non-limiting, embodiment illustrated in FIG. 3, the aqueous stream comprising 1,4-butanediol and its co-products 301 is fed into a counter-current extraction unit 322. Said extraction unit is also fed with first solvent stream 323, which is contacted with stream 301 in a counter-current manner. A first solvent rich stream 312, containing one of the desired materials present, is removed. Subsequently, a second solvent rich stream 316, containing another of the desired materials present, and a third solvent rich stream 320, containing a third desired material are removed. A residual stream 321 is also removed for further purification, recycle or disposal.
As with the embodiment shown in FIG. 2, if all of 1,4-butanediol, tetrahydrofuran, γ-butyrolactone and n-butanol are present in suitably high quantities, a fourth extraction step may be used to separate the fourth desired material present. In this embodiment, a fourth solvent rich stream, containing the fourth desired material will be removed.
Optionally, an additional aqueous stream 324 may be added to the extraction unit 322. The residual stream 321 may then be recycled and added to aqueous stream 324 before it is fed into extraction unit 322. In this case, the feed stream 301 may be located at any height (tray) in extraction unit 322, even below the first 312 or second 320 alcohol rich streams.
In this embodiment, as with that described in FIG. 2, which material is extracted at each point will depend on the solvent used and any temperature profile present.
EXAMPLES Example 1
An aqueous stock solution was prepared containing 7.1 wt % tetrahydrofuran (THF) and 16.5 wt % 1,4-butanediol (BDO).
Example 2
5 gram of the stock solution described in Example 1 solution was contacted with 4 gram of dimethylcyclohexylamine. After separation of the layers, the organic and water phase were analyzed by GC. The organic phase contained 60% of the THF present and 40% of BDO present.

Claims (11)

The invention claimed is:
1. A process for the recovery of 1, 4-butanediol and at least one co-product selected from γ-butyrolactone, n-butanol and tetrahydrofuran from an aqueous stream, said process comprising the steps of providing the aqueous stream, providing a first solvent stream, combining said aqueous stream with said first solvent stream and recovering at least a portion of the 1, 4-butanediol and at least a portion of at least one of the co-products by liquid-liquid extraction wherein at least one co-product is tetrahydrofuran.
2. The process according to claim 1, wherein the aqueous stream is derived from a reaction product stream from a process for the production of 1, 4-butanediol and/or THF.
3. The process according to claim 1, wherein at least a portion of the 1, 4-butanediol and at least a portion of at least one of the co-products present are recovered by liquid-liquid extraction by a process comprising the steps of extracting at least a portion of the 1, 4-butanediol and at least a portion of at least one of the co-products present into the solvent and separating a first 1, 4-butanediol, co-products and solvent rich stream, leaving a first residual stream wherein at least one co-product is tetrahydrofuran.
4. The process according to claim 3, wherein the 1, 4-butanediol, co-products and solvent rich stream is then separated into a 1, 4-butanediol rich stream, a solvent rich stream and separate streams each rich in one of the co-products present by distillation.
5. The process according to claim 1, wherein at least a portion of the 1, 4-butanediol and at least a portion of each of the co-products present are recovered by liquid-liquid extraction by a process comprising extracting at least a portion of the 1, 4-butanediol into a solvent stream to provide a first 1, 4-butanediol and solvent rich stream; extracting at least a portion of the THF, if present, into a solvent stream to provide a first THF and solvent rich stream; extracting at least a portion of the γ-butyrolactone, if present, into a solvent stream to provide a first γ-butyrolactone and solvent rich stream; and extracting at least a portion of the n-butanol, if present, into a solvent stream to provide a first n-butanol and solvent rich stream, leaving a residual stream.
6. The process according to claim 1, wherein the solvent is an amine.
7. The process according to claim 6, wherein the solvent is a tertiary amine.
8. The process according to claim 6, wherein the solvent is selected from the group consisting of dimethyl-cyclohexyl amine, methyl cyclohexyl amine, N-methyl piperidine, triethylamine, tripropylamine, or a combination thereof.
9. The process according to claim 1, wherein the solvent is an alcohol.
10. The process according to claim 9, wherein the solvent is selected from n-butanol, n-pentanol and octanols.
11. The process according to claim 3, wherein any residual stream is recycled to the process in which the 1, 4-butanediol was formed.
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WO2017042289A1 (en) * 2015-09-10 2017-03-16 Shell Internationale Research Maatschappij B.V. Process for the production of 1,4-butanediol and tetrahydrofuran from furan
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Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2831801A (en) 1952-09-18 1958-04-22 Allied Chem & Dye Corp Process for the recovery of isobutanol from alcoholic mixtures
US4032583A (en) * 1975-08-08 1977-06-28 Petro-Tex Chemical Corporation Purification of 1,4-butanediol
US4032683A (en) 1976-09-27 1977-06-28 Phillips Petroleum Company Structural member and method of making same
US4081354A (en) 1975-11-03 1978-03-28 Uop Inc. Liquid-liquid extraction process
US4447643A (en) 1981-09-28 1984-05-08 National Distillers And Chemical Corporation Process for recovering oxygenated organic compounds from dilute aqueous solutions employing liquid extraction media
US4966658A (en) 1989-12-27 1990-10-30 Lloyd Berg Recovery of ethylene glycol from butanediol isomers by azeotropic distillation
US5387731A (en) 1991-12-20 1995-02-07 Exxon Chemical Patents Inc. Process for the removal of green oil from a hydrocarbon stream
US5423955A (en) 1994-07-05 1995-06-13 Lloyd Berg Separation of propylene glycol from 1,2-butanediol by azeotropic
WO1995019946A1 (en) 1994-01-24 1995-07-27 Chemical Research & Licensing Company Method for removing contaminants from hydrocarbon streams
EP0844228A2 (en) 1996-11-21 1998-05-27 Daicel Chemical Industries, Ltd. Processes for separating adamantanols
CN1216973A (en) 1996-03-29 1999-05-19 科瓦内加工技术有限公司 Purification method of 1,4-butanediol
US6023003A (en) 1998-01-13 2000-02-08 Reading & Bates Development Co. Process and system for recovering glycol from glycol/brine streams
WO2002022593A1 (en) 2000-09-14 2002-03-21 International Furan Technology (Pty) Limited Gaseous acid catalysis
US20050072663A1 (en) 2002-10-28 2005-04-07 Geraldine Laborie Method of regenerating an aqueous glycol solution containing salts
US20090171129A1 (en) 2007-12-27 2009-07-02 Gevo, Inc. Recovery of higher alcohols from dilute aqueous solutions
JP2009256294A (en) 2008-04-14 2009-11-05 Epsilon Co Ltd Economical process for producing anhydrous alcohol or gasohol using ether solvent
WO2010080038A1 (en) 2009-01-08 2010-07-15 Aker Process Systems As Method for regeneration and reclamation of mono ethylene glycol using a vacuum slip stream
WO2011028131A1 (en) 2009-09-02 2011-03-10 Aker Process Systems As Device and method for recovering meg
US8067214B2 (en) 2007-03-16 2011-11-29 Genomatica, Inc. Compositions and methods for the biosynthesis of 1,4-butanediol and its precursors
US20110312050A1 (en) 2011-07-28 2011-12-22 Uop Llc Continuous catalytic generation of polyols from cellulose
CN102295384A (en) 2011-06-16 2011-12-28 博瑞德（南京）净化技术有限公司 1,4-butanediol chemical waste water treatment technology
US20120018293A1 (en) 2009-01-26 2012-01-26 Statoil Petroleum As Process for hydrate inhibitor regeneration
WO2012041990A1 (en) 2010-09-30 2012-04-05 Shell Internationale Research Maatschappij B.V. Process for producing furfural
US20120184783A1 (en) 2010-08-18 2012-07-19 Eastman Chemical Company Process for the separation and purification of a mixed diol stream
CN102643165A (en) 2011-06-28 2012-08-22 中国科学院大连化学物理研究所 Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars
WO2012130316A1 (en) 2011-03-31 2012-10-04 Metabolic Explorer Method for purifying mpg (monopropylene glycol) from a fermentation broth
WO2013011462A2 (en) 2011-07-20 2013-01-24 Aker Process Systems As Hydrate inhibitor recovery process
US20130284584A1 (en) 2012-01-10 2013-10-31 Shanghai Research Institute Of Petrochemical Technology, Sinopec Process for separating ethylene glycol and 1, 2-butanediol
CN103396290A (en) 2013-07-08 2013-11-20 吉林化工学院 Novel process for separating ethylene glycol and 1,2-butanediol
CN103664522A (en) 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method with heat integration function for separating ethylene glycol from 1,2-butylene glycol
CN103772147A (en) 2012-10-25 2014-05-07 中国石油化工股份有限公司 Separating method for ethylene-glycol and 1,2-butanediol
CN103772148A (en) 2013-07-08 2014-05-07 吉林化工学院 Novel method for separating mixture of ethylene glycol and 1, 2-butanediol by adopting azeotropic distillation and extraction coupling technologies

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2831801A (en) 1952-09-18 1958-04-22 Allied Chem & Dye Corp Process for the recovery of isobutanol from alcoholic mixtures
US4032583A (en) * 1975-08-08 1977-06-28 Petro-Tex Chemical Corporation Purification of 1,4-butanediol
US4081354A (en) 1975-11-03 1978-03-28 Uop Inc. Liquid-liquid extraction process
US4032683A (en) 1976-09-27 1977-06-28 Phillips Petroleum Company Structural member and method of making same
US4447643A (en) 1981-09-28 1984-05-08 National Distillers And Chemical Corporation Process for recovering oxygenated organic compounds from dilute aqueous solutions employing liquid extraction media
US4966658A (en) 1989-12-27 1990-10-30 Lloyd Berg Recovery of ethylene glycol from butanediol isomers by azeotropic distillation
US5387731A (en) 1991-12-20 1995-02-07 Exxon Chemical Patents Inc. Process for the removal of green oil from a hydrocarbon stream
WO1995019946A1 (en) 1994-01-24 1995-07-27 Chemical Research & Licensing Company Method for removing contaminants from hydrocarbon streams
US5423955A (en) 1994-07-05 1995-06-13 Lloyd Berg Separation of propylene glycol from 1,2-butanediol by azeotropic
CN1216973A (en) 1996-03-29 1999-05-19 科瓦内加工技术有限公司 Purification method of 1,4-butanediol
EP0844228A2 (en) 1996-11-21 1998-05-27 Daicel Chemical Industries, Ltd. Processes for separating adamantanols
US6023003A (en) 1998-01-13 2000-02-08 Reading & Bates Development Co. Process and system for recovering glycol from glycol/brine streams
WO2002022593A1 (en) 2000-09-14 2002-03-21 International Furan Technology (Pty) Limited Gaseous acid catalysis
US20050072663A1 (en) 2002-10-28 2005-04-07 Geraldine Laborie Method of regenerating an aqueous glycol solution containing salts
US8067214B2 (en) 2007-03-16 2011-11-29 Genomatica, Inc. Compositions and methods for the biosynthesis of 1,4-butanediol and its precursors
US20090171129A1 (en) 2007-12-27 2009-07-02 Gevo, Inc. Recovery of higher alcohols from dilute aqueous solutions
CN101959568A (en) 2007-12-27 2011-01-26 格沃股份有限公司 Reclaim higher alcohol from dilute aqueous solution
JP2009256294A (en) 2008-04-14 2009-11-05 Epsilon Co Ltd Economical process for producing anhydrous alcohol or gasohol using ether solvent
WO2010080038A1 (en) 2009-01-08 2010-07-15 Aker Process Systems As Method for regeneration and reclamation of mono ethylene glycol using a vacuum slip stream
US20120018293A1 (en) 2009-01-26 2012-01-26 Statoil Petroleum As Process for hydrate inhibitor regeneration
WO2011028131A1 (en) 2009-09-02 2011-03-10 Aker Process Systems As Device and method for recovering meg
US20120184783A1 (en) 2010-08-18 2012-07-19 Eastman Chemical Company Process for the separation and purification of a mixed diol stream
WO2012041990A1 (en) 2010-09-30 2012-04-05 Shell Internationale Research Maatschappij B.V. Process for producing furfural
WO2012130316A1 (en) 2011-03-31 2012-10-04 Metabolic Explorer Method for purifying mpg (monopropylene glycol) from a fermentation broth
CN102295384A (en) 2011-06-16 2011-12-28 博瑞德（南京）净化技术有限公司 1,4-butanediol chemical waste water treatment technology
CN102643165A (en) 2011-06-28 2012-08-22 中国科学院大连化学物理研究所 Method for producing ethylene glycol and 1,2-propylene glycol through continuous hydrocrackin of sugars
WO2013011462A2 (en) 2011-07-20 2013-01-24 Aker Process Systems As Hydrate inhibitor recovery process
US20110312050A1 (en) 2011-07-28 2011-12-22 Uop Llc Continuous catalytic generation of polyols from cellulose
US20130284584A1 (en) 2012-01-10 2013-10-31 Shanghai Research Institute Of Petrochemical Technology, Sinopec Process for separating ethylene glycol and 1, 2-butanediol
CN103664522A (en) 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method with heat integration function for separating ethylene glycol from 1,2-butylene glycol
CN103772147A (en) 2012-10-25 2014-05-07 中国石油化工股份有限公司 Separating method for ethylene-glycol and 1,2-butanediol
CN103396290A (en) 2013-07-08 2013-11-20 吉林化工学院 Novel process for separating ethylene glycol and 1,2-butanediol
CN103772148A (en) 2013-07-08 2014-05-07 吉林化工学院 Novel method for separating mixture of ethylene glycol and 1, 2-butanediol by adopting azeotropic distillation and extraction coupling technologies

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
"Extraction THeory and General Procedure." Adapted from Mohrig. (c) Apr. 1, 2013. Available from: <https://web.archive.org/web/20130401055038/http://academics.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/Techniques/Extraction/extraction_n.html >. *
Ghanadzadeh, et al.: Experimental and Theoretical Study of the Phase Equilibria in Ternary Aqueous Mixtures of 1,4-Butanediol with Alcohols at 298.2 K j Chem Eng., 2009, 54, pp. 1009-1014.
Guan, Weihong: Heilongjiang Petrochemical Technology, vol. 11, No. 4, Dec. 31, 2000 The preparation and application of 1,4-butanediol, pp. 9-11, 1-16, 18-19.
Hoydonckx, H.E., et al.: Furfural and Derivatives, in Ulmann's Encyclopedia or Industrial Chemistry, vol. 16, pp. 285-313, 2012.
Lange, Jean-Paul, et al.; Furfural-A Promisign Platform for Lignocellulosic Biofuels, ChemSusChem 2012, pp. 150-166.
Lange, Jean-Paul, et al.; Furfural—A Promisign Platform for Lignocellulosic Biofuels, ChemSusChem 2012, pp. 150-166.
Lange, J-P., et al.: Furfural-A Promising Platform for Lignocellulosic Biofuels; ChemSusChem, 5, pp. 150-166, 2012, Wiley-VCH Verlag GmBH & Co. KGaA, Weinheim.
Lange, J-P., et al.: Furfural—A Promising Platform for Lignocellulosic Biofuels; ChemSusChem, 5, pp. 150-166, 2012, Wiley-VCH Verlag GmBH & Co. KGaA, Weinheim.
Watson, James M.: Butane-1,4-diol from Hydrolytic Reduction of Furan, Ind. Eng. Chem. Prod. Res. Develop., vol. 12, No. 4, pp. 310-311, 1973.
Zeitsch, Karl. J.: The chemistry and technology of furfural and its many by-products. Elsevier, 2000.

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